The complex sym-cis-(Dioxo(2,2'-bipyridine)bis(pyridine)rhenium (v) has recently been synthesized and its structure has been determined. The complex represents the first confirmed hexacoordinate cis-dioxo complex of rhenium and is one of only a handful of d2 metal complexes known to possess the cis-dioxo ligand configuration. The dioxo complexes of rhenium (V) are of interest in general because of their multielectron electrochemical behavior, persistent (in some instances) photophysical activity, and possible redox catalytic activity. The method appears to be general for synthesizing various substituted pyridyl and bipyridyl complexes. Keywords: Hexafluorophosphates, Ligands, Synthesis, Pyridyl complex, BPY, PY.